Petroleum Sulfonate Research Articles

Interaction of Stabilized Alkylbenzene Sulfonate Surfactants on the Nanoscale with Water-Wet and Oil-Wet Carbonate Surfaces under High-Salinity and High-Temperature Conditions: A QCM-D Study.

Understanding the interactions of surfactants and wettability alteration of surfaces is important for many fields, including oil and gas recovery. This work utilizes the quartz crystal microbalance with dissipation to study the interaction of stabilized linear and branched alkylbenzene sulfonates (ABSs), among the most cost-efficient industrial surfactants, with water- and oil-wet calcite surfaces under high-salinity and high-temperature conditions. Confocal laser scanning microscopy is also used to study the effect of the type of ABS on their interaction with oil-wet calcite surfaces. Experiments demonstrate that vesicles made of linear and branched ABSs interact differently with both water- and oil-wet surfaces. Therefore, surfactant formulations made of ABSs for high-salinity applications can further be improved for advantageous wettability properties by varying the hydrophobic chain of the surfactants. When interacting with a water-wet surface, both types of vesicles adsorb onto the surface as is. Upon dilution, however, vesicles made of linear ABS stay adsorbed as is, and vesicles made of branched ABSs disassemble and produce a layered structure with altered wettability. Linear ABSs show greater efficiency in desorbing oil from the oil-wet calcite. The results of this study demonstrate an improved method for studying and understanding the interaction of surfactant formulations with water- and oil-wet surfaces. This approach could significantly benefit applications in which wettability alteration of surfaces is of great interest and facilitate the implementation of low-cost surfactants based on petroleum sulfonates.

Interfacial properties of petroleum sulfonate for oil displacement in separation process

In order to provide valuable information for the separation process of petroleum sulfonate and the mixing rule of petroleum sulfonate components, the methods of water extraction and column chromatography were used to separate non-sulfonated oil and petroleum sulfonate components, respectively. The effects of oil separation rate, source of crude oil, and composition of petroleum sulfonate on oil–water interfacial tension (IFT) were investigated. The results showed that the oil–water IFT of petroleum sulfonate products for oil displacement was affected by many factors. The presence of a small amount of non-sulfonated oil in petroleum sulfonate had positive synergistic interaction on the reduction of IFT. Reasonable mixture of petroleum sulfonate components with different polarities could avoid chromatographic separation and improve the interfacial activity of products. When the oil separation rate was 70%, the IFT between oil and water was the lowest, which served as a reference for the separation of non-sulfonated oil. Under the same oil displacement conditions, crude oil from different blocks had a greater impact on oil–water IFT. The ultra-low IFT appeared when intermediate petroleum sulfonate and water-soluble petroleum sulfonate were compounded with 3:1.

Design and Characterization of Naphthalene Ionic Liquids.

Surfactants have a great number of applications. Among these chemicals, petroleum sulfonates have been widely used due to their effectiveness in reducing interfacial tension. This is the case of sodium octylnaphthalene sulfonate which is a solid with a very low solubility in water. To overcome these drawbacks, this work aimed to synthesize new surface active ionic liquids based on a naphthalene sulfonate anion and traditional cations of these salts (imidazolium, pyrrolidinium, and pyridinium). The new chemicals showed high thermal stability, ionic liquid nature, and a stronger surfactant character than the original naphthalene. Moreover, they were found to be water soluble which greatly facilitates their application in the form of aqueous formulations. 1-Hexyl-3-methylimidazolium 4-(n-octyl)naphthalene-1-sulfonate showed the best capacity to reduce water-air and water-oil interfacial tension.

Effects of surface modification Nano-SiO2 and its combination with surfactant on interfacial tension and emulsion stability

Nano-silica (Nano-SiO2) particles have some limitations in their application as an oil displacement agent due to the easy aggregation characteristics. Therefore, it is necessary to modify the particle surface to enhance its dispersibility. A silane coupling agent (KH570) was used to organically modify Nano-silica, the relationship between the dosage of KH570 with the zeta potential, contact angle, particle size, sedimentation rate of modified Nano-SiO2 particles before and after modification was studied. And a displacement system (KH570-G-Nano-SiO2/PS) was fabricated by compounding modified Nano-SiO2 particles with the petroleum sulfonate (PS) molecules, the interfacial tension, emulsification property of the system with crude oil were systematically investigated, finally the synergistic effect of modified particles on the reduction of interfacial tension was explored. Results showed that when the dosage of KH570 was 5 %, the wettability of the particles changed from hydrophilic to hydrophobic, and the dispersion stability was significantly improved. The modified Nano-SiO2 (0.2 %)/PS (0.3 %) system can reduce the oil/water interfacial tension to 5.42 × 10−3 mN/ m. At this point, zeta potential of the system was 54.8 mV, and the stability of the emulsion prepared by this system reached its best level. The modification of Nano-SiO2 particles and the mechanism of reducing the oil/water interfacial tension after compounded with petroleum sulfonate (PS) is analyzed. The modification degree of Nano-SiO2 particles has great influence on the interfacial tension of the system compounding with surfactant.

Effect of Electrolyte on Synergism for Reducing Interfacial Tension between Betaine and Petroleum Sulfonate

To expound the mechanisms responsible for the effect of electrolyte on the interfacial tensions (IFTs) of mixed solutions containing zwitterionic surfactant alkyl sulfobetaine (ASB) and anionic sur...

Studies on interfacial interactions between petroleum sulfonate and sulfobetaine molecules by rheological measurements

The dilational rheological properties of aqueous solutions of anionic surfactant petroleum sulfonate (KPS), zwitterionic surfactant alkyl sulfobetaine (ASB) and their mixtures have been investigated at the kerosene-water interface by the oscillating drop method. The influences of time, dilational frequency, bulk concentration and interfacial pressure on the dilational properties have been expounded. The experimental results show that the nature of film containing anionic surfactant KPS molecules is determined by the diffusion-exchange process between the bulk and the interface. On the other hand, the in-film process, such as the orientation change of hydrophilic groups, controls the properties of adsorption layers formed by betaine ASB molecules. The dilational rheological behaviors of KPS-ASB mixtures are close to those of ASB. In addition, the complex system gets the largest dilational modulus at higher bulk concentration, due to a synergistic effect between KPS and ASB caused by electrostatic attraction. The mixed adsorption of KPS and ASB may lead to more compact films and result in higher interfacial dilational modulus at optimum ratio of adsorbed KPS to ASB molecules. The mixed adsorption of KPS and ASB molecules may lead to more compact film and result in larger interfacial dilational elasticity at higher concentration.

Recognition and characterization of active fractions from petroleum sulfonate

Petroleum sulfonates are widely used in chemical flooding in China. The samples are complicated and not all the fractions are effective. To recognize effective fraction with excellent interfacial activity and emulsifying property, a preparative liquid chromatography technology was adopted to perform the fraction separation for petroleum sulfonate. Structural composition, interfacial activity，emulsifying property and flooding efficiency of obtained fractions were also analyzed and discussed. It was shown that petroleum sulfonate can be effectively separated into different fractions with obvious structural differences, among which one fraction with the most excellent interfacial activity and the emulsifying property was recognized. The average molecular weight and molecular weight distribution range of this active fraction were 455.5 and 428–468, respectively, which are both crucial for activities. Alkylbenzene dicyclohexane sulfonates, alkyl indan sulfonates, and alkyl naphthalene sulfonates are major structure types, and alkyl chain length is mainly distributed between 12–15, 15–17 and 15–17 respectively. Besides, this active fraction is universal, and it can produce ultralow interfacial tension (~10−3 mN/m) and good emulsifying property against different crude oils including Xinjiang, Changqing, Liaohe Oilfields, etc. in China. The developed technology herein can be used to track and confirm the characteristics and/or active fraction in petroleum sulfonate accurately.

The alternative solutions of bagasse waste utilization to improve recovery factors in reservoir with high salinity

Surfactant injection is one of the EOR methods used to increase oil recovery. Using of surfactants is intended to reduce the interface tension between oil and water. The types of surfactants commonly used are oil-based surfactants, such as petroleum sulfonate. This condition causes the price of surfactants very dependent on oil prices. As efficient alternative, research on plant-based surfactants sourced from nature is being developed. Like the type of surfactant that will be used in this study is Sodium Lignosulfonate (NaLS) sourced from bagasse waste. The purpose of this study is to add reference of the characteristics of the NaLS surfactant to be used optimally. The screenings in this experiment were Aqueous Stability test, phase behaviour test, and IFT test on 1.5% NaLS concentration and high salinity 75,000 ppm Nacl. The results of aqueous stability test are transparent, the results of phase behaviour test are middle phase emulsion with an emulsion percent of 8.75%, and the results of IFT test obtained value of 1.98 mN/m. Based on these results, surfactants meet the screening parameters so can proceed to the injection stage for determine the value of recovery factor. Recovery factor result for NaLS bagasse waste based surfactant injection is 4.74%.

Synthesis of sulfonate of alkylated extract of FCC slurry for enhancing oil recovery

To extend the application of the extracted oil from FCC slurry, the alkylated extract of FCC slurry was sulfonated by concentrated sulfuric acid to prepare petroleum sulfonate for oil displacement. The sulfonation processing parameters were optimized and the effects of the sulfonate products on enhancing oil recovery were investigated. Under the optimized conditions, the produced petroleum sulfonate (PS) had lower critical micelle concentration (CMC) value (0.2 wt%) and higher surface activity (the surface tension was 31.53 mN·m−1) than the commercialized surfactants. Furthermore, the petroleum sulfonate was mixed with additive, whose interfacial tension could be decreased to 0.0038 mN·m−1 (0.2 wt% PS + 0.1 wt% Na2CO3). The mixture solution also had good oil displacement effect, which could enhance the recovery by 25.1%. Therefore, this sulfonate protocol could effective extend the environmental friendly applications of extract of FCC slurry with good market application prospects.

Nanofluid of Petroleum Sulfonate Nanocapsules for Enhanced Oil Recovery in High-Temperature and High-Salinity Reservoirs

Petroleum sulfonate (PS) salt surfactants that are insoluble in high-salinity water were encapsulated into 10–60 nm oil swollen micelles dispersed by a cocamidopropyl hydroxysultaine zwitterionic c...

Effect of Emulsification on Surfactant Partitioning in Surfactant‐Polymer Flooding

AbstractA laboratory surfactant‐polymer flooding experiment was performed to study the effect of emulsification on surfactant partitioning. The partition coefficient of petroleum sulfonates (KPS) after emulsification was significantly higher than that under static conditions. The partition coefficient of KPS gradually decreases with the increase of polymer concentration from 1000–3000 mg L−1, indicating that the increase of polymer concentration could protect KPS from the partition loss of emulsification. The lower the oil–water ratio, the higher the partition coefficient. The partition coefficient of KPS of resin and asphaltene was higher than that of crude oil. Alkanes, aromatics, and other polar components in crude oil have a significant influence on the partition of KPS.

The effect of diesel emulsification using sodium petroleum sulfonate on carbon flotation from fly ash

It is critical to separate carbon from fly ash due to its increasing amount being produced per year and component requirements for secondary utilizations. Flotation is an efficient technique to fulfill this task. Effects of diesel emulsification using sodium petroleum sulfonate on unburned carbon flotation from a fly ash sample were studied. Flotation tests showed that carbon recovery was increased from 41% to 86% using the emulsified collector at the same dosage level (0.5 kg/ton) as diesel. Zeta potential measurements indicated that both the carbon and emulsified collector droplets carried negative charges within the studied pH range. For fly ash particles with high carbon content, adsorption bands of carbonyl bond (CO) were detected in the FTIR spectra, which agreed with the XPS characterization findings. XPS analysis indicated that the emulsified diesel (ED) collector interacted more intensively with the surface carbon-oxygen groups relative to the normal diesel collector. Finally, the improved efficiency of ED is proved to be related to its polar groups and reduced oil droplet size. The polar groups of ED (mainly sulfonate) interacted with the surface oxygen containing groups (e.g., CO and COOH) through hydrogen bonding and Lewis acid base interaction.

Effect of the number of ethylene oxide units on the properties of synthesized tailor-made cationic gemini surfactants for oilfield applications

The solubility and heat stability of the surfactants are the most prominent features required for oilfield applications. Commercial surfactants such as petroleum sulfonate, polyoxyethylene ether, and alkyl benzyl sulfonate suffer because of stability issues under high salinity and high-temperature conditions. Herein, two new cationic amido-amine type poly(ethylene oxide) gemini surfactants containing lower and higher degree of ethoxylation were synthesized. It was observed that the addition of a sufficient number of ethylene oxide groups between the hydrophobic tail and the ionic head group of the cationic gemini surfactant significantly enhanced their solubility. The surfactant containing a higher degree of ethoxylation was found to be soluble in formation water and seawater. However, the surfactant with a lower degree of ethoxylation precipitated in formation water and seawater and hence was not studied further. Thermogravimetric analysis results of the surfactants containing a higher degree of ethoxylation exhibited degradation temperature above 300 °C that was greater than the typical reservoir temperature (90 °C). The structure characterization results of the aged sample of surfactant at 90 °C for 90 days demonstrated the survival of the original chemical structure, revealing a high long-time heat stability. The reduction in critical micelle concentration (CMC) was observed upon enhancing salt concentration, and the minimum CMC was noticed in seawater (3.91 × 10−5 mol/L). Rheological investigations revealed that the viscosity, as well as storage modulus, was reduced upon increasing the concentration of surfactant. The surfactant also exhibited superior foaming properties compared to the commercial surfactants. The cationic amido-amine type poly(ethylene oxide) gemini surfactants showed excellent surface and thermal properties and are potential candidates for oilfield applications such as enhanced oil recovery in harsh reservoir conditions.

Wax Inhibitor Screening by Differential Scanning Calorimeter for High Wax Content Crude Oil

In order to investigate the wax inhibition performance of various inhibitors different scanning calorimetric (DSC), a powerful and quickly technique having no request of sample pretreatment, has been used for investigation the thermal characteristics of the wax remover. According to the parameters such as wax appearance temperature (WAT), content of wax and rheology, it is found that the best wax removing rate can be reached to 457mg/L•h under 40°C with 150mg/L surfactant combination (fatty alcohol polyoxyethylene ether + calcium petroleum sulfonate + mixed alcohol).

Separation of non-sulfonated oil from industrial petroleum sulfonate

The non-sulfonated oil in industrial petroleum sulfonate was separated by centrifugal method and extraction method, respectively. The oil separation rates of each method were compared, and the effects of oil separation rates under different conditions on the purity of non-sulfonated oil were investigated. The purity information of non-sulfonated oil separated by different methods was analyzed by infrared spectroscopy. The experimental results showed that the oil separation rate of centrifugation was low, and the oil extraction rate was higher. The purity of non-sulfonated oil separated with alcohol–water solution as extractant was lower, while the purity of non-sulfonated oil separated by water extraction method was the highest, and the extractant was nontoxic and environmentally friendly. Water was preferred as extractant. Solvent ratio, temperature and pressure all had great influence on oil separation rate. The optimum conditions for SL petroleum sulfonate were: solvent ratio 1.5:1, 90 °C, atmospheric pressure, which the oil separation rate was 78.51%; and for DQ petroleum sulfonate, the optimum conditions were: solvent ratio 2:1, 90 °C, atmospheric pressure, which the oil separation rate was 79.86%. Non-sulfonated oil separated by water extraction had the least petroleum sulfonate, followed by ethanol single solvent extraction. Although the extraction efficiency of isopropanol aqueous solution and n-pentane was the highest, the content of petroleum sulfonate in non-sulfonated oil was the highest, which affected the product performance and should not be used.

An Experimental Approach to Formulate Lignin-Based Surfactant for Enhanced Oil Recovery

The higher cost of chemical surfactants has been one of the main reasons for their limited used in enhanced oil recovery (EOR) process. Hence, the reason for developing lignin-based surfactant is to lower the cost of chemicals as it does not tie to the price of crude oil as compared to petroleum-based surfactants. Besides, lignin is biodegradable and easily extracted from plant waste. The objectives of this study are to determine the formulations of the lignin-based surfactant for EOR applications and to determine the oil recovery performance of the formulated surfactants through surfactant flooding. The lignin-based surfactants were formulated by mixing the lignin with the amine (polyacrylamide or hexamethylenetetramine) and the surfactant sodium dodecylbenzenesulfonate in a 20,000 ppm NaCl brine. Interfacial tension (IFT) of the formulated lignin-based surfactant is measured at ambient temperature using the spinning drop method. The displacement experiments were conducted at room temperature in glass beads pack holders filled with glass beads, saturated with paraffin and brine. The results of the study showed that the best formulation of lignin-based surfactant is using hexamethylenetetramine as the amine, lignin, and sodium dodecylbenzenesulfonate at 2% total active concentration. The oil recovery and interfacial tension using the lignin amine system is comparable with the commercial petroleum sulfonate system.

Pilot Performance of Chemical Demulsifier on the Demulsification of Produced Water from Polymer/Surfactant Flooding in the Xinjiang Oilfield

Purification of produced water (PW) from polymer/surfactant flooding is a challenge for the petroleum industry due to the high emulsion stability. Demulsification using chemical demulsifiers has been expected to be an effective way to treat PW. In this paper, five cationic (branched quaternary ammonium chloride) and four nonionic (copolymer of propylene oxide and ethylene oxide) demulsifiers with different molecular weights were employed to test their respective demulsification performance in the treatment of PW from polymer/surfactant flooding. The cationic demulsifiers, in general, exhibited better performance than the nonionic ones and one cationic demulsifier (CP-1) exhibiting the best demulsification efficiency was further employed for a pilot experiment in the Xinjiang Oilfield. The oil content of PW could be successfully reduced from 128~7364 to less than 10 mg/L with a dosage of CP-1 for 350 mg/L and polyaluminum chloride (PAC, 30% w/w Al2O3) for 500 mg/L under ambient temperature (14~22 °C). At the same time, partially hydrolyzed polyacrylamide (HPAM) was removed from 176.9~177.1 to 2.8~3.9 mg/L while petroleum sulfonate was not removed too much (from 35.5~43.8 to 25.5~26.5 mg/L). The interfacial rheology analysis on simulated PW from HPAM/petroleum sulfonate flooding revealed that the addition of CP-1 led to a significant increase of the oil-water interfacial tension (from 7 to 15~20 mN/m) and zeta potential (from −32.5 to −19.7 mV). It was, thus, assumed that the decreased net charge on the dispersed oil droplets surface and weakened oil/water film due to the formation of complex between the cationic demulsifier and HPAM may have facilitated the destabilization of the emulsion. The result of this study is useful in better understanding the demulsification processes as well as selecting suitable demulsifiers in the treatment of PW from polymer/surfactant flooding.

Flotation studies of fluorite and barite with sodium petroleum sulfonate and sodium hexametaphosphate

The development of new collectors to separate fluorite from barite is urgently needed in mineral processing. In this study, the flotation behavior of fluorite and barite was studied using sodium petroleum sulfonate (SPS) as a collector with sodium hexametaphosphate (SHMP) as a depressant. The performance of reagents on minerals was interpreted by infrared spectroscopic analysis and zeta potential measurement. The flotation results showed that SPS performed well in a wide pH region (7–11) even at a low temperature (5°C), while the flotability of fluorite and barite were almost the same. At pH 11, the presence of SHMP obviously depressed fluorite rather than barite and SHMP exhibited good selective inhibition to fluorite. Fourier-transform infrared spectra and zeta potential results showed that: (1) SPS can adsorb on fluorite and barite surfaces and (2) SHMP had little effect on the adsorption of SPS on a barite surface, although it interfered with the adsorption of SPS on a fluorite surface through strong adsorption.

Challenge sodium lignosulfonate surfactants synthesized from bagasse as an injection fluid based on hydrophil liphophilic balance

The aim of this research is to obtain Sodium Lignosulfonate (SLS) surfactant from bagasse as an alternative petroleum sulfonate. The experimental method of the process SLS surfactant from bagasse through two processes, hydrolysis and sulphonation process. Then tested for its characteristics through FTIR test, LCMS test, NMR test and compatibility test. Based on the structure of the sodium lignosulfonate of bagasse with the empirical formula of lignosulfonate monomer is (C11H16O8S)n, have hydrophil and lipophyl groups. The calculation of Hydrophilic Lipophilic Balance (HLB), the synthesized SLS surfactant of bagasse has a HLB value of 11.62. From the compatibility test, this SLS surfactant have a good aquaeous stability, no turbidity, perfect soluble and clear. This SLS surfactant capable of water wet system and having the category as an O/W (Oil in Water) emulsion, indicating that the surfactant good dissolves in water. The mechanism of the synthesized SLS surfactant of the bagasse produces a good microemulsion between surfactant and oil. HLB is one of the parameters used to determine surfactant function. Based on the characteristic test and HLB value calculation it turns out that bagasse can be used as SLS surfactant. As an injection fluid in the EOR process, the SLS surfactant from bagasse has been in the function as O/W emulsion. So the use of lignosulfonate surfactant synthesized from bagasse is a challenge to be developed futher as a surfactant for the EOR process.

Separation of low polarity petroleum sulfonate: Eluant selection, characterization, and theoretical calculation

ABSTRACTPetroleum sulfonate is one of the most important surfactant in tertiary oil recovery process. Among complex components, low polarity petroleum sulfonate account for about 70% of total, but the main contributing components are still unknown, and the accurate evaluation method is imperative. In this work, low polarity petroleum sulfonate was successfully separated into four parts. All the separated samples were characterized by mass spectrometry, infrared spectroscopy, and nuclear magnetic resonance. The average carbon number, average aromatic carbon number, average saturated carbon number, and the average number of methyl were obtained. The results revealed that average relative molecular mass and branched degree are the main factors of varied polarities of petroleum sulfonate. What more, this study provided a reliable evaluation and characterization method of low polarity petroleum sulfonate.